Large‐area Free‐standing Metalloporphyrin‐based Covalent Organic Framework Films by Liquid‐air Interfacial Polymerization for Oxygen Electrocatalysis

Abstract

Synthesizing large‐area free‐standing covalent organic framework (COF) films is of vital importance for their applications but is still a big challenge. Herein, we reported the synthesis of large metalloporphyrin‐based COF films and their applications for oxygen electrocatalysis. The reaction of meso‐benzohydrazide‐substituted metal porphyrins with tris‐aldehyde linkers afforded free‐standing COF films at the liquid‐air interface. These films can be scaled up to 3000 cm2 area and display great mechanical stability and structural integrity. Importantly, the Co‐porphyrin‐based films are efficient for electrocatalytic O2 reduction and evolution reactions. A flexible, all‐solid‐state Zn‐air battery was assembled using the films and showed high performance with a charge–discharge voltage gap of 0.88 V at 1 mA cm−2 and high stability under bent conditions (0° to 180°). This work thus presents a strategy to synthesize functionalized COF films with high quality for uses in flexible electronics.

Dimensional engineering of covalent organic frameworks derived carbons for electrocatalytic carbon dioxide reduction

“…27 Then, the COFs with different metal porphyrin or various linker phthalocyanine cores were developed to catalyze the CO 2 RR. 3,[27][28][29][30][31][32][33][34][35][36][37][38][39] However, the difficult for designing and synthesizing the catalytic building units hindered us further exploring the new catalytic centers in COFs for CO 2 RR.…”

Graphene oxide-based large-area dynamic covalent interfaces

“…Large-area dynamic covalent interfaces (LDCIs) are capable of reversible structural adaptation and response to the variation of external surroundings, [1][2][3] making them highly promising candidates for various applications in molecular detection/ recognition, [4][5][6] biosensing, [7][8][9] drug loading/release, [10][11][12] and interfacial catalysis. [13][14][15] Over the past few decades, significant efforts have been devoted to constructing various dynamic materials [16][17][18] over a wide range of systems from polymers, [18][19][20][21][22][23][24][25][26] covalent organic frameworks, 14,15,27,28 and supramolecules 17,[29][30][31][32] to emulsions/foams, [33][34][35] in particular the introduction of dynamic covalent bonds (DCBs) into traditional materials, endowing them with many advanced dynamic characteristics, such as responsiveness, [35][36][37] selfadaptivity 36,38,…”

“…Large-area dynamic covalent interfaces (LDCIs) are capable of reversible structural adaptation and response to the variation of external surroundings, 1–3 making them highly promising candidates for various applications in molecular detection/recognition, 4–6 biosensing, 7–9 drug loading/release, 10–12 and interfacial catalysis. 13–15 Over the past few decades, significant efforts have been devoted to constructing various dynamic materials 16–18 over a wide range of systems from polymers, 18–26 covalent organic frameworks, 14,15,27,28 and supramolecules 17,29–32 to emulsions/foams, 33–35 in particular the introduction of dynamic covalent bonds (DCBs) into traditional materials, endowing them with many advanced dynamic characteristics, such as responsiveness, 35–37 self-adaptivity 36,38,39 and self-healing. 22,38,40,41 The key mechanism underlying the characteristics of these dynamic covalent materials (DCMs) is that DCBs can reversibly break and reform under defined conditions, 18,20,23 which combines the stability of covalent bonds and the dynamics of non-covalent bonds.…”

Fabrication of a Novel Co/CoO@Fe2V4O13 Composite Catalyst as a Photoanode for Enhanced Photoelectrochemical Water Oxidation

“…[12][13][14][15] For prospective PEC performance, designing and developing a highly effective and stable catalyst is crucial. Various materials as electrocatalysts [16][17][18][19] and photoelectrocatalysts [20] have been explored and optimized to enhance their efficiency using different strategies. A key challenge is to find novel, low-cost, and durable photocatalysts with suitable band positions.…”